Organohalogen compounds in blubber of Indo-Pacific bottlenose dolphin (Tursiops aduncus) and spinner dolphin (Stenella longirostris) from Zanzibar, Tanzania

Blubber samples of Indo-Pacific bottlenose (Tursiops aduncus) and spinner (Stenella longirostris) dolphins from Zanzibar, East Africa, were analyzed for a wide range of organohalogen compounds. Methoxylated polybrominated diphenyl ethers (MeO-BDEs), presumably biogenic, were found at higher concentrations than anthropogenic organochlorine pesticides (OCPs). Only traces of industrial pollutants, such as polychlorinated biphenyls, were detected. The OCP levels found off Zanzibar were lower than those reported from other regions while MeO-BDE levels were higher. The relative composition of the OCPs indicated recent use of lindane (γ-hexachlorocyclohexane) and aged residues of DDT and technical HCH. Placental transfer was estimated to 2.5% and 0.5% of the total burden of OCPs and MeO-BDEs, respectively. Overall transfer from mother to calf in Indo-Pacific bottlenose dolphins was estimated to 72% and 85% for the OCPs and MeO-BDEs burdens, respectively. Health effects of MeO-BDEs are not known, but structural similarities with well-known environmental toxins are cause for concern.     

Organochlorine pesticides accumulation and degradation products in vegetation samples of a contaminated area in Galicia (NW Spain)

The content of 21 organochlorine pesticides were studied in vegetation samples of a highly contaminated area by isomers of hexachlorocyclohexane (HCH) located close to a former industrial area in Galicia (NW Spain). Five species of plants were collected at different points of the contaminated area and the different parts of the plants were separated in order to study differences in accumulation capabilities. Samples were extracted employing microwave energy followed by a clean-up step using solid phase extraction and finally determined by GC–ECD. The results obtained show that the most abundant pesticides are HCHs isomers, being the main isomers β-HCH and -HCH in all samples whereas δ-HCH and γ-HCH were at lower levels. Some other pesticides such as p,p′-DDT, p,p′-DDD and p,p′-DDE were also present in much lower amount in some of the samples. Several degradation products of HCH were also identified in some samples by GC–MS.     

Persistent organic pollutants in cork used for production of wine stoppers

Owing to the lipophilic character of some components of cork and the long periods in the open air (during growth and barks storage), there is a risk of the cork becoming environmentally polluted. Moreover, cork stoppers are in contact with wines for periods ranging from a few months to several years; so they must maintain high levels of hygiene. The present work aims to investigate the level of PCBs, organochlorine pesticides, and PAHs in cork from different countries, used for the manufacturing of one-piece wine stoppers. Samples of cork were analysed using a multi-residue method. PCBs were not detected in all the samples; only a few samples contained detectable amounts of DDE; phenanthrene and anthracene were found in all the samples and fluoranthene in fewer cases. It was not possible to find a significant correlation between POPs concentration and origin of cork. Globally, the detected amounts are consistent with values found in foods, so the investigated cork show a suitable hygienic quality.     

Assessing the toxicity and teratogenicity of pond water in north-central minnesota to amphibians

BACKGROUND: Incidence of amphibian deformities have increased in recent years, especially in the northern region of the United States. While many factors have been proposed as being responsible for generating deformities (e.g., contaminants, ultraviolet radiation [UV], parasites), no single cause has been definitively established. METHODS: To determine whether waterborne chemicals are responsible for amphibian deformities in ponds in north-central Minnesota, we deployed semipermeable membrane devices (SPMDs) in an impacted and a reference site to accumulate lipophilic contaminants. We then exposed native tadpoles (northern leopard frogs; Rana pipiens) to the SPMD extracts combined with two agricultural pesticides (atrazine, carbaryl) at two levels of UV radiation. RESULTS AND DISCUSSION: UV radiation alone caused a slight increase in hatching success and tadpole growth rate. Deformity rate among hatchlings was high following exposure to SPMD extracts from the reference site in the absence of UV, suggesting that chemicals present at this site are broken down by UV to less harmful forms, or become less bioavailable. Conversely, impacted site SPMD extracts caused hatchling deformities only in the presence of UV, suggesting that UV potentiates the teratogenicity of the compounds present there. Impacted site SPMD extracts significantly increased the number of bony triangles among metamorphs, a common deformity observed at this site. The incidence of skin webbings increased significantly with SPMD extracts from both sites as well as with our pesticide control containing atrazine and carbaryl alone. CONCLUSIONS: Higher deformity rates among tadpoles reared in the presence of UV radiation and SPMD extracts from sites where deformities are common indicates a chemical compound (or compounds) in the water at this site may be causing the deformities. RECOMMENDATIONS AND OUTLOOK: It is important to examine the effects of chemical stressors in the presence of other natural stressors (e.g., UV radiation) to gain a better understanding of how multiple stressors work to impact amphibians and amphibian populations.     

Prospects and limitations of phytoremediation for the removal of persistent pesticides in the environment

The environmental problems that have arisen from the use of persistent pesticides in the past, and potential sources of further contamination have been discussed. The potential and limitations of phytoremediation for removal of pesticides in the environment have been reviewed. The enzymatic processes in plants that are known to be involved in phytodegradation of pesticides, and possibilities for enhancing them have also been discussed.     

Enantiomer fractions of chiral organochlorine pesticides and polychlorinated biphenyls in standard and certified reference materials

Enantiomeric ratios (ERs) and enantiomeric fractions (EFs) of a number of chiral organochlorine pesticides and PCB atropisomers were measured by chiral gas chromatography/mass spectrometry (GC/MS) in five standard (SRM) and certified (CRM) reference materials: SRM 1588a (organics in cod liver oil), SRM 1945 (organics in whale blubber), Marine Mammal Quality Assurance Exercise Control Material IV (NIST IV, organics in whale blubber), CRM trout, and CRM EC-5 (sediment). Target analytes were cis- and trans-chlordane, heptachlor exo-epoxide, oxychlordane, U82, MC5, MC6, MC7, o,p^′-DDT, and PCB congeners 91, 95, 136, 149, 174, 176, and 183. Measured ERs and EFs are in close agreement with the few literature values reported for some of these analytes in SRMs and CRMs. Chiral PCB ERs and EFs measured by one-dimensional chiral GC/MS were similar to values measured using multidimensional chiral GC/MS. Non-racemic chiral compositions are in agreement with known uptake and biotransformation in the respective environmental matrices. These values should aid in the quality assurance/quality control methodologies for chiral environmental chemistry using standardized reference materials.     

基于环境风险排序的流域优先污染物筛选

在流域生态环境治理中,确定治理水体的优先污染物是首先要考虑的问题.环境风险排序方法可利用污染物的毒性值与该污染的暴露浓度值的比值,快速对流域污染物进行风险排序,确定优先污染物.本文以有多年氟化工生产排放历史的大凌河为研究区域,分季节采集18个样点的水体表层样品,分析全氟辛基磺酸(PFOS)、全氟辛酸(PFOA)以及8种常见重金属,并搜集有关当地物种生态毒性的文献资料,确定其优先污染物.结果发现,2011~2016年间,大凌河水体PFOS和PFOA的中位值浓度分别在0.77~3.57 ng·L~(-1)、82.93~344 ng·L~(-1)之间,参照英国水环境对人体健康的潜在风险值发现其均低于标准限值.重金属和有机氯农药的浓度均低于国家Ⅳ级标准,但Hg和As的最高浓度高于Ⅲ级标准.大凌河环境风险值范围为1.42×10-6~2.3×10-2,环境风险排序结果为CuZnAsp,p'-DDEp,p'-DDTCdPbHgPFOAγ-HCHCrNiα-HCHPFOS.PFOS和PFOA的环境风险排序较为靠后,说明不是该地区需要优先控制的污染物,但长期风险累积不可忽视.Cu是未来大凌河生态环境治理的优先污染物,应重点控制包括造纸厂在内的主要工业企业的生产排放行为.     

低温碱性熔体脱氯解毒农药废物及氯盐的富集

以二氯苯酚为代表,采用NaOH-KOH混盐熔体对农药废物进行脱氯解毒处理.研究了温度、碱料比、反应时间等参数对脱氯效率的影响.结果表明,当NaOH和KOH摩尔比为1：1时,混盐的熔点较低,脱氯效果最好.提高碱料比和反应时间可以明显提高脱氯效率,当碱料比为20,反应时间为180min,温度为200℃时,二氯苯酚的脱氯效率达到80.1%.采用多种手段对熔渣进行了分析,红外光谱显示二氯苯酚中的苯环和C-Cl键被破坏,形成了多种氧化中间体.X射线衍射图谱显示反应过程中生成的氯化氢有效保留在碱性熔体中形成氯盐并逐渐富集.     

Teratological effects of pesticides in vertebrates: a review

Abstract

In the last decades, the use and misuse of pesticides in the agriculture have increased, having a severe impact on ecosystems and their fauna. Although the various effects of pesticides on biodiversity have been already documented in several studies, to our knowledge no consistent overview of the impact of pesticides in vertebrates, both terrestrial and aquatic, is available. In this review, we try to present a concise compilation of the teratogenic effects of pesticides on the different classes of vertebrates – mammals, birds, reptiles, amphibians and fish.     

Sensitized photooxygenation of the fungicide furalaxyl

BACKGROUND: The photolysis of pesticides is of high current interest since light is one of the most important abiotic factors which are responsible for the environmental fate of these substances and may induce their conversion into noxious products. The action of light can also be mediated by oxygen and synthetic or naturally occurring substances which act as sensitizers. Our objective in this study was to investigate the photochemical behaviour of the systemic fungicide furalaxyl in the presence of oxygen and various sensitizers, and to compare the toxicity of the main photoproduct(s) to that of the parent compound. Previous reports on the direct photolysis of the pesticide demonstrated a very slow degradation and the only identified photoproducts were N-2,6-xylyl-D,L-alaninare and 2,6-dimethylaniline. METHODS: Solutions of furalaxyl in CH3CN were photooxygenate using a 500W high-pressure mercury lamp (through a Pyrex glass filter, lambda>300 nm) or a 650W halogen lamp or sunlight and the proper sensitizer. When sunlight was used, aqueous solutions were employed. The photodegradation was checked by NMR and/or GC-MS. The photoproducts were spectroscopically evidenced and, when possible, isolated chromatographically. Acute toxicity tests were performed on the rotifer Brachionus calyciflorus, the crustacean cladoceran Daphnia magna and the anostracan Thamnocephalus platyurus, while chronic toxicity tests (sublethal endpoints) comprised a producer, the alga Pseudokirchneriella subcapitata and the crustacean Ceriodaphnia dubia, as a consumer. RESULTS AND DISCUSSION: In the presence of both oxygen and sensitizer, furalaxyl underwent rapid photochemical transformations mainly to N-disubstituted formamide, maleic anhydride and a 2(5H)-furanone derivative. The formation of these products was rationalized in terms of a furan endoperoxide intermediate derived from the reaction of furalaxyl with active dioxygenated species (singlet oxygen, superoxide anion or ground state oxygen). The 2(5H)-furanone exhibited a higher toxicity than the parent compound. CONCLUSION: This work reports the first data on the photosensitized oxygenation of furalaxyl with evidence of the high tendency of the pesticide to undergo photodegradation under these conditions leading, among other things, to a 2(5H)-furanone, which is more toxic than the starting furalaxyl towards aquatic organisms. RECOMMENDATIONS AND OUTLOOK: Investigation highlights that the photolytic fate of a pesticide, although quite stable to direct photoreaction due to its low absorption of solar radiation at ground level, can be significantly influenced in the environment by the presence of substances with energy or electron-transfer properties as natural dyes, e.g. chlorophyll, or synthetic pollutants, e.g. polycyclic aromatic hydrocarbons (PAH).